EP1828300B1 - Regulation de la viscosite pour dispersions fluoropolymeres aqueuses a teneur en tensioactif fluore reduite, par l'ajout de tensioactif cationique - Google Patents
Regulation de la viscosite pour dispersions fluoropolymeres aqueuses a teneur en tensioactif fluore reduite, par l'ajout de tensioactif cationique Download PDFInfo
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- EP1828300B1 EP1828300B1 EP05854900A EP05854900A EP1828300B1 EP 1828300 B1 EP1828300 B1 EP 1828300B1 EP 05854900 A EP05854900 A EP 05854900A EP 05854900 A EP05854900 A EP 05854900A EP 1828300 B1 EP1828300 B1 EP 1828300B1
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- dispersion
- fluorosurfactant
- anion exchange
- exchange resin
- stabilized
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
Definitions
- This invention relates to removing fluorosurfactant from aqueous fluoropolymer dispersions and more particularly relates to controlling of the viscosity of the resulting dispersions.
- Aqueous fluoropolymer dispersions are typically manufactured in an aqueous dispersion polymerization employing anion fluorosurfactants as a polymerization aid, the fluorosurfactants functioning as a non-telogenic dispersing agent.
- anion fluorosurfactants functioning as a polymerization aid
- the dispersions are usually subjected to a concentration step to increase the fluoropolymer solids concentration in the dispersion.
- the dispersion is concentrated with the aid of a nonionic surfactant as taught in Marks et al., U.S.
- Patent 3,037,953 and in Holmes, U. S. Patent 3,704,272 to raise the solids from nominally 35 wt% in the raw dispersion to about 60 wt% in the concentrated dispersion.
- Miura et al., U.S. 6,153,688 discloses a similar process.
- Anionic fluorosurfactants and nonionic surfactants are usually present in the concentrated dispersions.
- Patent 4,282,162 (Kuhls ). Kuhls teaches recovery or fluorinated emulsifiers dissolved in the aqueous phase after coagulation of the polymer from the dispersion or in aqueous polymer dispersions to be concentrated.
- anion exchange processes such as in US 2003/0220 442 A1 , the anionic fluorosurfactant is removed by the anion exchange resin from a stabilized dispersion containing nonionic surfactant.
- the viscosity levels can be higher than in dispersions containing fluorosurfactant and can be unacceptably high for some end uses.
- the invention provides a process for reducing the viscosity of a stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion by reducing the fluorosurfactant content of the stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion to a predetermined level and adding cationic surfactant.
- the fluorosurfactant content of a stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion is reduced by contacting the stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion with an anion exchange resin.
- the stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion for treatment in accordance with the present invention is made by dispersion polymerization (also known as emulsion polymerization).
- the aqueous fluoropolymer dispersion is a stabilized fluorosurfactant-containing aqueous fluoropolymer dispersion which means that it contains sufficient nonionic surfactant to prevent coagulation of the dispersion when the fluorosurfactant content is reduced.
- the nonionic surfactant may already be present or may be added for stabilization prior to treatment according to the invention.
- aqueous fluoropolymer dispersions are useful in coating or impregnating compositions and to make cast films.
- Fluoropolymer dispersions are comprised of particles of polymers made from monomers wherein at least one of the monomers contains fluorine.
- the fluoropolymer of the particles of the aqueous dispersions used in this invention is independently selected from the group of polymers and copolymers of tifluoroethylene, hexafluoropropylene, monochlorotrifluoroethylene, dichlorodifluoroethylene, tetrafluoroethylene, perfluoroalkyl ethylene monomers, perfluoro(alkyl vinyl ether) monomers, vinylidene fluoride, and vinyl fluoride.
- the invention is especially useful when the fluoropolymer component of the dispersion is polytetrafluoroethylene (PTFE) including modified PTFE which is not melt-processible.
- PTFE polytetrafluoroethylene
- Modified PTFE refers to copolymers of TFE with such small concentrations of comonomer that the melting point of the resultant polymer is not substantially reduced below that of PTFE.
- concentration of such comonomer is preferably less than 1 weight %, more preferably less than 0.5 weight %.
- the modified PTFE contains a small amount of comonomer modifier which improves film forming capability during baking (fusing), such as perfluoroolefin, notably hexafluoropropylene (HFP) or perfluoro(alkyl vinyl) ether (PAVE), where the alkyl group contains 1 to 5 carbon atoms, with perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE) being preferred.
- Chlorotrifluoroethylene (CTFE), perfluorobutyl ethylene (PFBE), or other monomer that introduces bulky side groups into the molecule are also included.
- the PTFE typically has a melt creep viscosity of at least 1 x 10 9 Pa•s. Such high melt viscosity indicates that the PTFE does not flow in the molten state and therefore is not melt-processible.
- PTFE and modified PTFE are frequently sold in dispersion form and transported in shipping containers and the process of the invention can be readily employed for reducing the fluorosurfactant content of such dispersions.
- the fluoropolymer component of the dispersion may be melt-processible.
- melt-processible it is meant that the polymer can be processed in the molten state (i.e., fabricated from the melt into shaped articles such as films, fibers, and tubes etc. that exhibit sufficient strength and toughness to be useful for their intended purpose).
- melt-processible fluoropolymers include copolymers of tetrafluoroethylene (TFE) and at least one fluorinated copolymerizable monomer (comonomer) present in the polymer in sufficient amount to reduce the melting point of the copolymer substantially below that of TFE homopolymer, polytetrafluoroethylene (PTFE), e.g., to a melting temperature no greater than 315°C.
- TFE tetrafluoroethylene
- PTFE polytetrafluoroethylene
- fluoropolymers include polychlorotrifluoroethylene, copolymers of tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE).
- Preferred comonomers with of TFE are perfluoroolefin having 3 to 8 carbon atoms, such as hexafluoropropylene (HFP), and/or perfluoro(alkyl vinyl ether) (PAVE) in which the linear or branched alkyl group contains 1 to 5 carbon atoms.
- Preferred PAVE monomers are those in which the alkyl group contains 1, 2, 3 or 4 carbon atoms, and the copolymer can be made using several PAVE monomers.
- TFE copolymers include FEP (TFE/HFP copolymer), PFA (TFE/PAVE copolymer), TFE/HFP/PAVE wherein PAVE is PEVE and/or PPVE and MFA (TFE/PMVE/PAVE wherein the alkyl group of PAVE has at least two carbon atoms).
- the melt-processible copolymer is made by incorporating an amount of comonomer into the copolymer in order to provide a copolymer which typically has a melt flow rate of about 1-100 g/10 min as measured according to ASTM D-1238 at the temperature which is standard for the specific copolymer.
- melt viscosity will range from 10 2 Pa•s to about 10 6 Pa•s, preferably 10 3 to about 10 5 Pa•s measured at 372°C by the method of ASTM D-1238 modified as described in U.S. Patent 4,380,618 .
- Additional melt-processible fluoropolymers are the copolymers of ethylene or propylene with TFE or CTFE, notably ETFE, ECTFE and PCTFE.
- Further useful polymers are film forming polymers of polyvinylidene fluoride(PVDF) and copolymers of vinylidene fluoride as well as polyvinyl fluoride (PVF) and copolymers of vinyl fluoride.
- a typical process for the aqueous dispersion polymerization of preferred polymer PTFE is a process wherein TFE vapor is fed to a heated reactor containing fluorosurfactants, paraffin wax and deionized water. If desired, a chain transfer agent can also be employed to reduce the molecular weight to the desired level.
- a free-radical initiator solution is added and, as the polymerization proceeds, additional TFE is added to maintain the pressure. The exothermic heat of reaction is removed by circulating cooling water through the reactor jacket. After several hours, the feeds are stopped, the reactor is vented and purged with nitrogen, and the raw dispersion in the vessel is transferred to a cooling vessel.
- Paraffin wax is removed and polymer dispersion is transferred to a dispersion concentration operation which produces stabilized dispersions which are useful for the practice of the present invention.
- the dispersion concentration operation the dispersion is concentrated with the aid of a nonionic surfactant as taught in Marks et al., U.S. Patent 3,037,953 , and in Holmes, U.S. Patent 3,704,272 to raise the solids from nominally 35 wt% to about 60 wt%.
- Miura et al., U.S. 6,153,688 discloses a similar process.
- Aromatic alcohol ethoxylates can be used as the nonionic surfactant but, because there is concern about possible environmental harm from aromatic compounds, preferred nonionic surfactants are aliphatic alcohol ethoxylates. Suitable nonionic surfactants include any of a variety of aliphatic alcohol ethoxylates or mixtures thereof which provide the desired cloud point during concentration and which provide desired properties in the dispersion, e.g., low bum off temperature, dispersion stability, etc.
- Especially preferred nonionic surfactants are a compound or mixture of compounds of the formula: R(OCH 2 CH 2 ) n OH wherein R is a branched alkyl, branched alkenyl, cycloalkyl, or cycloalkenyl hydrocarbon group having 8-18 carbon atoms and n is an average value of 5 to 18.
- the dispersion polymerization of melt-processible TFE copolymers is similar except that one or more comonomers are added to the batch initially and/or introduced during polymerization.
- a telogen such as a hydrocarbon is employed to control the molecular weight to achieve the desired melt flow of the polymer for the intended purpose.
- the same dispersion concentration operation performed with the aid a nonionic surfactant as used for PTFE dispersions can be used for TFE copolymer dispersions.
- Stabilized fluorosurfactant-containing dispersions suitable for use in the practice of the present invention can be made prior to concentration by adding nonionic surfactants to raw dispersion (after wax removal referred to above). It is desirable to use the same nonionic surfactants that will be used for concentration and nonionic surfactants for this purpose are described above. Nonionic surfactant is added to the raw dispersion under mild agitation conditions in approximately the same concentrations as is used for concentration, 2 to 6 % based on the weight of the dispersion.
- Stabilized fluorosurfactant-containing fluoropolymer dispersions with solids content of 15 to 70 wt% are treated in accordance with the invention.
- the solids content is at least 25 wt%, more preferably at least 30 wt%, and most preferably at least 35 wt%.
- the anionic fluorosurfactant in the fluorosurfactant-containing dispersions to be reduced in this process is a non-telogenic, anionic dispersing agent, soluble in water and comprising an anionic hydrophilic group and a hydrophobic portion.
- the hydrophobic portion is an aliphatic fluoroalkyl group containing at least four carbon atoms, all except at most one of which, and that one the closest to the solubilizing .. group, bearing at least two fluorine atoms, the terminal carbon atom bearing in addition an atom consisting of hydrogen or fluorine.
- fluorosurfactants are used as a polymerization aid for dispersing and, because they do not chain transfer, they do not cause formation of polymer with undesirable short chain length.
- An extensive list of suitable fluorosurfactants is disclosed in Patent 2,559,752 to Berry.
- the fluorosurfactant is a perfluorinated carboxylic acid having 6-10 carbon atoms and is typically used in salt form.
- Suitable fluorosurfactants are ammonium perfluorocarboxylates, e.g., ammonium perfluorocaprylate or ammonium perfluorooctanoate.
- the fluorosurfactants are usually present in the amount of 0.02 to 1 wt % with respect to the amount of polymer formed.
- the cationic surfactant used in accordance with the present invention is a quaternary ammonium halide or hydroxide, preferably a compound of the formula: where R 1 is a long chain alkyl hydrocarbon, an alkylated aryl hydrocarbon and R 2 , R 3 , and R 4 are alkyl groups, preferably having 1-16 carbon atoms.
- the alkyl groups may contain cyclic structures and may be either linear or branched and Y can be F, Cl, Br or OH.
- R 1 is an alkyl group containing between 8 and 28 carbon atoms, more preferably between 12 and 18 carbon atoms.
- R 2 , R 3 , and R 4 are the same or different and are selected from the group comprising methyl or ethyl.
- Two especially effective surfactants are dodecyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide (CTMAB).
- CTMAB is also known as hexadecyl trimethyl ammonium bromide.
- the cationic surfactants preferably used in accordance with the invention preferably have the advantage of being completely volatile at PTFE sintering temperatures. Therefore, they do not introduce residues into sintered PTFE when the dispersions in accordance with the invention are applied in coating and film applications.
- the amount of the cationic surfactant sufficient to reduce dispersion viscosity to a predetermined desirable level depends on a number of factors including the nature of the polymer, the amount of residual fluorosurfactant if present, the solids content of the dispersion and the amount and type of non-ionic surfactant present. Determining an optimum level of cationic surfactant for commercial production can easily be ascertained empirically by one skilled in the art using samples of the dispersion. In some cases, a small amount of a cationic surfactant may initially increase the viscosity of the dispersion before enough is added to reduce the viscosity.
- the viscosity is reduced significantly by the addition of amounts of the cationic surfactant in slight excess over the small amount which produces a viscosity increase but larger amounts do not provide further significant decrease in viscosity.
- the cationic surfactant is added in an amount of at least about 100 ppm, preferably about 100 ppm to about 1000 ppm based on the weight of the dispersion.
- the amount of cationic surfactant added reduces the viscosity of the concentrated dispersion to less than about 50 cP, more preferably less than about 40 cP, and most preferably less than about 30 cP.
- the anion exchange resins for use in accordance with the preferred embodiment of the present invention can be either strongly basic or weakly basic.
- Suitable weakly basic anion exchange resins contain primary, secondary amine, or tertiary amine groups.
- Suitable strongly basic anion exchange resin contain quaternary ammonium groups.
- weakly basic resins are useful because they can be regenerated more easily, strongly basis resins are preferred when it is desired to reduce fluorosurfactant to very low levels and for high utilization of the resin.
- Strongly basic ion exchange resins also have the advantage of less sensitivity to the pH of the media.
- Strongly basic cation exchange resins have an associated counter ion and are typically available in chloride or hydroxyl ion form but are readily converted to other forms if desired.
- Anion exchange resins with hydroxyl, chloride, sulfate, and nitrate can be used for the removal of the fluorosurfactant but anion exchange resins in the form of a hydroxyl counter ion are preferred to prevent the introduction of additional anions and to increase pH during anion exchange because a high pH, i.e., greater than 9, is desirable in the product prior to shipping to inhibit bacterial growth.
- Examples of suitable commercially-available strong base anion exchange resins with quaternary ammonium groups with a trimethylamine moiety include DOWEX® 550A, US Filter A464-OH, SYBRON M-500-OH, SYBRON ASB1-OH, PUROLITE A-500-OH, Itochu TSA 1200, AMBERLITE® IR 402.
- Examples of suitable commercially-available stong base anion exchange resins with quaternary ammonium groups with a dimethyl ethanol amine moiety include US Filter A244-OH, AMBERLITE® 410, DOWEX® MARATHON A2, and DOWEX® UPCORE Mono A2.
- Anion exchange resin preferably used in the process of the present invention is monodisperse. More preferably, the anion exchange resin beads have a number average size distribution in which 95% of the beads have a diameter within plus or minus 100 ⁇ m of the number average bead diameter.
- the monodisperse anion exchange resin has a particle size which provides a suitable pressure drop through the bed. Very large beads are fragile and prone to breakage. Very small ion exchange beads are susceptible to tight particle packing resulting in tortuous channels in the bed. This can result in high shear conditions in the bed.
- Preferred ion exchange resin has a number average bead size about 450 to about 800 ⁇ m, more preferably, the ion exchange resin beads have a number average bead diameter of about 550 to about 700 ⁇ m.
- the present invention permits reducing the fluorosurfactant content of a fluorosurfactant-containing dispersion to a predetermined level, preferably a level no greater than about 300 ppm, more preferably a predetermined level no greater than about 100 ppm, especially a predetermined level no greater than about 50 ppm.
- the fluorosurfactant content can be reduced by any of the procedures as have been described by the prior art.
- One method for removal of fluorosurfactants from fluoropolymer dispersions is disclosed in U.S. Patent 4,369,266 and includes the addition of a stabilizing surfactant followed by concentration by ultrafiltration.
- the fluorosurfactant is removed by adsorption onto an ion exchange resin as taught has been taught in U.S. Patent 3,882,153 (Seki et al ) and U.S. Patent 4,282,162 (Kuhls ).
- Nonionic surfactants are added prior to contact with the anion exchange resin as discussed above.
- any of a variety of techniques which bring the dispersion in contact with the anion exchange resin can be used to carrying out ion exchange of the process.
- the process can be carried out by addition of ion exchange resin bead to the dispersion in a stirred tank followed by separation of dispersion from the anion exchange resin beads by filtration.
- Another suitable method is to pass the dispersion through a fixed bed of anion exchange resin instead of using a stirred tank. Flow can be upward or downward through the bed and no separate separation step is needed since the resin remains in the fixed bed.
- the contacting of the dispersion is performed at a temperature which is sufficiently high to facilitate the rate of ion exchange and to reduce the viscosity of the dispersion but being below a temperature at which the anion exchange resin degrades at a detrimentally high rate.
- the process should be run at a temperature below the cloud point of the non-ionic surfactant to prevent phase separation during the ion exchange process.
- Upper treatment temperature will vary with the type of polymer employed. Typically, temperatures will be between 20°C and 80°C. Preferably, the temperature is between about 45°C and 65°C, more preferably between about 50°C and 60 °C.
- the fluorosurfactant can be recovered from the anion exchange resin if desired or the resin with the fluorosurfactant can be disposed of in an environmentally acceptable method, e.g., by incineration. If it is desired to recover the fluorosurfactant, the fluorosurfactant may be removed from resin by elution. Elution of fluorosurfactant adsorbed on the anion exchange resin is readily achieved when weak base resins are used by use of ammonia solution as demonstrated by Seki in U.S. Patent 3,882,153 , by a mixture of dilute mineral acid with organic solvent (e.g., HCl/ethanol) as demonstrated by Kuhls in U.S.
- organic solvent e.g., HCl/ethanol
- Patent 4,282,162 or by strong mineral acids such as sulfuric acid and nitric, transferring the adsorbed fluorinated carboxylic acid to the eluent.
- the fluorosurfactant in the eluent in high concentration can easily be recovered in the form of a pure acid or in the form of salts by common methods such as acid- " deposition, salting out, or other forms of concentration, etc.
- the cationic surfactant is added after removal of the fluorosurfactant because the cationic surfactant may form a complex with the fluorosurfactant, hampering its removal.
- the significant increase in viscosity which is observed in some reduced fluorosurfactant dispersions upon concentration can be avoided if the cationic surfactant is added prior to concentration.
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Abstract
Claims (12)
- Procédé pour la réduction de la teneur en tensioactif fluoré d'une dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée comprenant:la mise en contact de ladite dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée avec une résine échangeuse d'anions pour réduire la teneur en tensioactif fluoré à un niveau prédéterminé, ladite dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée possédant une teneur en solides de 15 à 70% en poids et une teneur en tensioactif non ionique de 2 à 6% en poids, sur la base du poids de la dispersion;la séparation de ladite résine échangeuse d'anions à partir de ladite dispersion après la réduction de la teneur en tensioactif fluoré; caractérisé par:la concentration de ladite dispersion après la séparation de ladite résine échangeuse d'anions à partir de ladite dispersion;l'ajout d'un tensioactif cationique à ladite dispersion après le retrait du tensioactif fluoré et avant ladite concentration, ledit tensioactif cationique étant un halogénure ou un hydroxyde d'ammonium quaternaire.
- Procédé selon la revendication 1, dans lequel ledit tensioactif cationique est ajouté dans une quantité d'au moins 100 ppm sur la base du poids de la dispersion.
- Procédé selon la revendication 1, dans lequel ledit tensioactif cationique est ajouté dans une quantité de 100 ppm à 1000 ppm sur la base du poids de la dispersion.
- Procédé selon la revendication 1, dans lequel ladite dispersion stabilisée possède une teneur en solides d'au moins 25% en poids.
- Procédé selon la revendication 1, dans lequel ladite dispersion stabilisée possède une teneur en solides d'au moins 30% en poids.
- Procédé selon la revendication 1, dans lequel ladite dispersion stabilisée possède une teneur en solides d'au moins 35% en poids.
- Procédé selon la revendication 1, dans lequel ladite résine échangeuse d'anions possède des groupes fonctionnels choisis dans le groupe comprenant des groupes d'amine primaire, d'amine secondaire, d'amine tertiaire et d'ammonium quaternaire.
- Procédé selon la revendication 1, dans lequel ladite résine échangeuse d'anions comprend des groupes d'ammonium quaternaire.
- Procédé selon la revendication 1, dans lequel ladite résine échangeuse d'anions est sous forme d'hydroxyde.
- Procédé selon la revendication 1, dans lequel ladite mise en contact de ladite dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée avec une résine échangeuse d'anions réduit la teneur en tensioactif fluoré à un niveau prédéterminé de moins de 300 ppm.
- Procédé selon la revendication 1, dans lequel ladite mise en contact de ladite dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée avec une résine échangeuse d'anions réduit la teneur en tensioactif fluoré à un niveau prédéterminé de moins de 100 ppm.
- Procédé selon la revendication 1, dans lequel ladite mise en contact de ladite dispersion fluoropolymère aqueuse contenant un tensioactif fluoré stabilisée avec une résine échangeuse d'anions réduit la teneur en tensioactif fluoré à un niveau prédéterminé de moins de 50 ppm.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US63831004P | 2004-12-22 | 2004-12-22 | |
PCT/US2005/046260 WO2006069101A1 (fr) | 2004-12-22 | 2005-12-19 | Regulation de la viscosite pour dispersions fluoropolymeres aqueuses a teneur en tensioactif fluore reduite, par l’ajout de tensioactif cationique |
Publications (2)
Publication Number | Publication Date |
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EP1828300A1 EP1828300A1 (fr) | 2007-09-05 |
EP1828300B1 true EP1828300B1 (fr) | 2011-02-16 |
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EP05854900A Not-in-force EP1828300B1 (fr) | 2004-12-22 | 2005-12-19 | Regulation de la viscosite pour dispersions fluoropolymeres aqueuses a teneur en tensioactif fluore reduite, par l'ajout de tensioactif cationique |
Country Status (6)
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US (2) | US20060135681A1 (fr) |
EP (1) | EP1828300B1 (fr) |
JP (1) | JP4961352B2 (fr) |
CN (1) | CN101087838B (fr) |
DE (1) | DE602005026447D1 (fr) |
WO (1) | WO2006069101A1 (fr) |
Families Citing this family (20)
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US20060135681A1 (en) * | 2004-12-22 | 2006-06-22 | Cavanaugh Robert J | Viscosity control for reduced fluorosurfactant aqueous fluoropolymer dispersions by the addition of cationic surfactant |
US7666927B2 (en) * | 2004-12-22 | 2010-02-23 | E.I. Du Pont De Nemours And Company | Removing fluorosurfactant from aqueous fluoropolymer dispersions using anion exchange polymer with functional groups resistant to degradation to trialkylamines |
US7390448B2 (en) * | 2005-08-05 | 2008-06-24 | E.I. Du Pont De Nemours And Company | Spinning low fluorosurfactant fluoropolymer dispersions |
US20070207273A1 (en) * | 2006-03-02 | 2007-09-06 | Jeffrey Todd English | Rapid drying of fluoropolymer dispersion coating compositions |
US7754287B2 (en) * | 2006-05-31 | 2010-07-13 | E. I. Du Pont De Nemours And Company | Process for forming filled bearings from fluoropolymer dispersions stabilized with anionic polyelectrolyte dispersing agents |
US20080264864A1 (en) | 2007-04-27 | 2008-10-30 | 3M Innovative Properties Company | PROCESS FOR REMOVING FLUORINATED EMULSIFIER FROM FLUOROPOLMER DISPERSIONS USING AN ANION-EXCHANGE RESIN AND A pH-DEPENDENT SURFACTANT AND FLUOROPOLYMER DISPERSIONS CONTAINING A pH-DEPENDENT SURFACTANT |
PL2459641T3 (pl) | 2009-07-31 | 2017-04-28 | 3M Innovative Properties Company | Kompozycje fluoropolimeru zawierającego związek poliolu oraz sposoby ich wytwarzania |
CN102575017A (zh) * | 2009-10-16 | 2012-07-11 | 旭硝子株式会社 | 聚沉加工用聚四氟乙烯水性分散液的制造方法及聚沉加工用聚四氟乙烯水性分散液 |
GB2481985A (en) * | 2010-07-13 | 2012-01-18 | 3M Innovative Properties Co | Removal of fluoroorganic anions from an aqueous phase |
EP2409998B1 (fr) | 2010-07-23 | 2015-11-25 | 3M Innovative Properties Company | Polymères PTFE à point de fusion élevé pour un traitement par fusion pour obtenir des articles formés |
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EP3284762A1 (fr) | 2016-08-17 | 2018-02-21 | 3M Innovative Properties Company | Fluoropolymeres comprenant tetrafluoroethylene et un ou plusieurs perfluorés allyle ether comonomères |
DE202017003084U1 (de) | 2017-06-13 | 2017-09-19 | 3M Innovative Properties Company | Fluorpolymerdispersion |
WO2018229659A1 (fr) | 2017-06-13 | 2018-12-20 | 3M Innovative Properties Company | Polytétrafluoroéthylène modifié et dispersion aqueuse contenant ce dernier |
EP3527634A1 (fr) | 2018-02-15 | 2019-08-21 | 3M Innovative Properties Company | Fluoropolymères et dispersions de fluoropolymère |
US11248130B2 (en) | 2018-04-20 | 2022-02-15 | Ecp Incorporated | Vehicle interior protective coating |
KR20220024226A (ko) * | 2019-06-26 | 2022-03-03 | 크로마포라 에이비 | 물로부터 pfas의 제거 방법 |
CN112707877B (zh) * | 2020-12-26 | 2022-08-23 | 中海油天津化工研究设计院有限公司 | 一种用于渣油高效降黏的油溶性降黏剂及制备方法 |
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BE475854A (fr) * | 1946-09-05 | |||
US2559752A (en) * | 1951-03-06 | 1951-07-10 | Du Pont | Aqueous colloidal dispersions of polymers |
US3037953A (en) * | 1961-04-26 | 1962-06-05 | Du Pont | Concentration of aqueous colloidal dispersions of polytetrafluoroethylene |
US3882153A (en) * | 1969-09-12 | 1975-05-06 | Kureha Chemical Ind Co Ltd | Method for recovering fluorinated carboxylic acid |
US3704272A (en) * | 1970-09-15 | 1972-11-28 | Du Pont | Concentration of polytetrafluoroethylene aqueous dispersion |
DE2903981A1 (de) * | 1979-02-02 | 1980-08-07 | Hoechst Ag | Rueckgewinnung fluorierter emulgatorsaeuren aus basischen anionenaustauschern |
DE2908001C2 (de) * | 1979-03-01 | 1981-02-19 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Herstellung konzentrierter Dispersionen von Fluorpolymeren |
JP2509826B2 (ja) * | 1991-03-28 | 1996-06-26 | 多木化学株式会社 | 酸化第二セリウムゾル |
JP3346090B2 (ja) * | 1995-03-31 | 2002-11-18 | ダイキン工業株式会社 | ポリテトラフルオロエチレン水性分散液組成物及びその用途 |
TW494125B (en) * | 1997-07-11 | 2002-07-11 | Rohm And Haas Compary | Preparation of fluorinated polymers |
DE19824615A1 (de) * | 1998-06-02 | 1999-12-09 | Dyneon Gmbh | Verfahren zur Rückgewinnung von fluorierten Alkansäuren aus Abwässern |
DE19857111A1 (de) * | 1998-12-11 | 2000-06-15 | Dyneon Gmbh | Wäßrige Dispersionen von Fluorpolymeren |
WO2000061696A1 (fr) * | 1999-04-07 | 2000-10-19 | Daikin Industries, Ltd. | Dispersion aqueuse hydrophobe et oléophobe |
DE19933696A1 (de) * | 1999-07-17 | 2001-01-18 | Dyneon Gmbh | Verfahren zur Rückgewinnung fluorierter Emulgatoren aus wässrigen Phasen |
US7279522B2 (en) * | 2001-09-05 | 2007-10-09 | 3M Innovative Properties Company | Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant |
US6855137B2 (en) * | 2002-03-07 | 2005-02-15 | Visionary Biomedical, Inc. | Catheter shaft with coextruded stiffener |
JP2004307524A (ja) * | 2002-03-29 | 2004-11-04 | Jsr Corp | フッ素含有オレフィン系重合体、硬化性樹脂組成物及び反射防止膜 |
EP1364972B1 (fr) * | 2002-05-22 | 2006-08-30 | 3M Innovative Properties Company | Procédé de réduction de la teneur en surfactant fluoré dans des dispersions aqueuses de fluoropolymére |
EP1441014A1 (fr) * | 2003-01-22 | 2004-07-28 | 3M Innovative Properties Company | Dispersion aqueuse d'un polymère fluoré comprenant un polymère fluoré thermoprocessable avec un contenu réduit de surfactants fluorés |
EP1452571B1 (fr) * | 2003-02-28 | 2005-08-17 | 3M Innovative Properties Company | Dispersion de fluoropolymère contenant pas ou peu d'agent tensioactif fluore à faible poids moléculaire |
ITMI20040031A1 (it) * | 2004-01-14 | 2004-04-14 | Solvay Solexis Spa | Processo per la preparazione di dispersori di fluoropolimeri |
US20060135681A1 (en) * | 2004-12-22 | 2006-06-22 | Cavanaugh Robert J | Viscosity control for reduced fluorosurfactant aqueous fluoropolymer dispersions by the addition of cationic surfactant |
-
2005
- 2005-12-02 US US11/293,778 patent/US20060135681A1/en not_active Abandoned
- 2005-12-19 JP JP2007548403A patent/JP4961352B2/ja not_active Expired - Fee Related
- 2005-12-19 WO PCT/US2005/046260 patent/WO2006069101A1/fr active Application Filing
- 2005-12-19 DE DE602005026447T patent/DE602005026447D1/de active Active
- 2005-12-19 EP EP05854900A patent/EP1828300B1/fr not_active Not-in-force
- 2005-12-19 CN CN2005800445127A patent/CN101087838B/zh not_active Expired - Fee Related
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2009
- 2009-07-13 US US12/501,610 patent/US8329836B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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CN101087838B (zh) | 2010-12-08 |
JP2008525590A (ja) | 2008-07-17 |
US20090275693A1 (en) | 2009-11-05 |
EP1828300A1 (fr) | 2007-09-05 |
WO2006069101A1 (fr) | 2006-06-29 |
CN101087838A (zh) | 2007-12-12 |
DE602005026447D1 (de) | 2011-03-31 |
US8329836B2 (en) | 2012-12-11 |
JP4961352B2 (ja) | 2012-06-27 |
US20060135681A1 (en) | 2006-06-22 |
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